EP0077977A2 - Verfahren zur Entfernung Hydroxy und/oder Merkapto substituierten Kohlenwasserstoffen aus Kohleflüssigkeiten - Google Patents

Verfahren zur Entfernung Hydroxy und/oder Merkapto substituierten Kohlenwasserstoffen aus Kohleflüssigkeiten Download PDF

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Publication number
EP0077977A2
EP0077977A2 EP82109463A EP82109463A EP0077977A2 EP 0077977 A2 EP0077977 A2 EP 0077977A2 EP 82109463 A EP82109463 A EP 82109463A EP 82109463 A EP82109463 A EP 82109463A EP 0077977 A2 EP0077977 A2 EP 0077977A2
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EP
European Patent Office
Prior art keywords
phase
alkanolamine
aqueous
naphtha
coal
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Withdrawn
Application number
EP82109463A
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English (en)
French (fr)
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EP0077977A3 (de
Inventor
Clifford Ward
Charles A. Johnson, Iii
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Ashland LLC
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Ashland Oil Inc
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Publication date
Application filed by Ashland Oil Inc filed Critical Ashland Oil Inc
Publication of EP0077977A2 publication Critical patent/EP0077977A2/de
Publication of EP0077977A3 publication Critical patent/EP0077977A3/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention is concerned with separating hydroxy-, and/or mercapto-substituted hydrocarbons from admixture with coal liquids.
  • the present invention is concerned with separating phenolic compounds, and/or mercaptans which are in admixture with coal liquids boiling below about 400°F.
  • the treated coal liquids, according to the present invention can then be processed to form desirable combustible fuels, such as gasoline.
  • the impurities removed from the coal liquids, such as phenolic compounds can be obtained for subsequent use.
  • coal liquid naphthas generally contain at least about 3.5% and mostly at least about 10% by weight of phenolic compounds. These quantities of phenolic compounds, if not significantly reduced prior to such processes as catalytic cracking, can significantly affect the process in an adverse manner. The phenolic compounds tend to poison and/or reduce the catalyst activity of the catalyst employed in such processes.
  • the present invention is concerned with a process for separating hydroxy-substituted hydrocarbons and/or thio-substituted hydrocarbons from admixture with coal liquids.
  • the coal liquids treated according to the process of the present invention boil below about 400°F.
  • the process includes contacting the admixture with an aqueous composition of a water-miscible alkanolamine.
  • the aqueous composition contains at least about 40% by weight of-the alkanolamine. This contact results in the formation of a two-phase mixture.
  • the two-phase mixture is then separated into an aqueous extract phase and a naphtha-raffinate phase.
  • the aqueous extract phase is admixed with additional water in order to increase the water content to about 70 to about 85% by weight. This results in the formation of a second naphtha phase and a second aqueous extract phase.
  • the second naphtha phase and second aqueous extract phase are then separated from each other.
  • the second aqueous extract phase is then treated in order to regenerate the aqueous alkanolamine and obtain the hydroxy-substituted hydrocarbons, and/or the thio-substituted hydro- carbons removed from the liquid coal naphtha.
  • Figure 1 is a flow diagram of a sequence of steps for carrying out the process of the present invention.
  • Figure 2 is a schematic of apparatus useful in carrying out the extraction stage of the present invention.
  • the coal liquids treated according to the present invention boil below about 400°F, and preferably about 80 to about 400°F.
  • the coal liquids usually contain hydroxy-substituted hydrocarbons in amounts of at least about 3.5%, and mostly about 7.5% to about 10.0% by weight of the coal liquid. Moreover, such generally contains at least about 0.01%, and mostly at least about 0.25% by weight of thio-substituted hydrocarbon compounds, such as thiophenol.
  • the predominant hydroxy-substituted hydro- carbons present in the coal liquids treated according to the present invention are hydroxy-substituted aromatic hydrocarbons and especially mononuclear phenolic compounds, such as phenol and alkyl-substituted phenols, such as orthocresol, metacresol, paracresol, and the xylenols, such as 3,4-xylenol, 3,5-xylenol, 2,4-xylenol, 2,6-xylenol, 2,3-xylenol, and 2,5-xylenol.
  • the coal liquids treated according to the present invention can contain substantial amounts of carboxylic acids which are concomitantly removed along with the hydroxy- and/or thio-substituted hydrocarbons.
  • the coal extract, from which the coal liquid naphthas treated according to the present invention are obtained can be produced by a number of well-known liquifying methods, such as the extraction of coal by hydrogen-donor solvents, SRC deashing process, and the catalytic hydrogenation of coal in a liquid solvent.
  • the coal liquid naphthas treated according to the present invention are obtained by the direct catalytic hydroliquidification process generally referred to as "H-Coal".
  • H-Coal is a direct catalytic hydroliquidification process developed by Hydrocarbon Research, Inc.
  • the H-Coal process generally involves initially crushing, drying and slurring the coal with a process-derived oil and pumping such at the reactor pressure, wherein it is mixed with hydrogen and fed to the reactor.
  • the catalyst employed is in the form of an ebullating bed.
  • the reactor typically operates at a temperature of about 450°C and a pressure of about 3000 psig.
  • One particular hydrogen donor solvent involves contacting the coal with a hydrogen-donor solvent at a temperature of about 700°F to about 850°F and a pressure of about 350 psig to about 1000 psig, either in the presence of or in the absence of extraneously added molecular hydrogen.
  • An extraction period of from about 1 hour to about 2 hours is usually employed.
  • the product in the extraction zone includes a liquid extract phase and a solid undissolved residue.
  • the extract may be first flushed to remove naphtha and lighter materials or may be charged directly to a hydrocracking zone. In-either event, the higher constituents are hydrocracked to produce naphtha which can be separately treated according to the present invention or which can be combined with the flash naphtha before such treatment.
  • Suitable hydrocracking conditions include contact with a cobalt- molvbdenate catalyst and hydrogen at a temperature of about 750°F and a pressure of about 2000 psi g , a weight hourly space velocity of about 0.8 pound of liquid per pound of catalyst per hour, and a hydrogen feed rate of about 50,000 SCF/B.
  • the liquid coal naphtha is contacted with an aqueous composition of a water-miscible alkanolamine.
  • the aqueous composition contains at least about 40% by weight, and preferably about 50% to about 60% by weight of the alkanolamine.
  • the alkanolamine can be a primary, secondary of tertiary amine and is preferably a monoamine.
  • Each of the alkanol groups of the amine preferably contain a maximum of four carbon atoms and a single hydroxyl group. Examples of some alkanolamines are monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, triisopropanolamine and diisopropanolamine.
  • the preferred amines are monoethanolamine and monopropanolamine. Mixtures of amines can be employed.
  • the amount of alkanolamine employed is generally at least about 0.01 to about 2.0 parts per part of liquid coal naphtha, and preferably about 1 part per ten parts by volume cf liquid coal naphtha.
  • the aqueous alkanolamine is preferably contacted with the liquid coal naphthas by countercurrent flow.
  • An example of a suitable contact apparatus is a Ycrk-Scheibel Column (see Fig. 2) whereby the aqueous alkanolamine is introduced via conduit 1, the licuid coal naphtha is introduced via conduit 2, the coal naphtha raffinate is removed via conduit 3, and the aqueous alkanolamine phenol extract is removed via conduit 4.
  • Coal liquids can be recycled to the treatment if desired via ccnduit 5.
  • the column contains stirring means 6 to facilitate contact and contact means 7.
  • the contact means 7 can be stainless steel wire mesh. Of course, it is understood that other means of contact between the aqueous alkanolamine and liquid coal naphthas can be employed.
  • the particular York-Scheibel Column shown is about 40 inches long and about one inch inside diameter. As noted from Figure 2, the column contains nine mixing stages 8, and ten stainless steel coalescing stages 7. The stirrer can typically be operated at about 250 RPM.
  • the naphtha raffinate phase can then be subjected to further processing in order to produce combustible fluids, such as gasoline.
  • the aqueous extract phase includes the hydroxy-substituted hydrocarbons, and/or mercapto-substituted hydro-carbons, and carboxylic acids initially present in the liquid coal naphthas. Such impurities are in the form of salts with the alkanolamine employed.
  • the aqueous extract phase also includes some liquid coal naphthas.
  • the aqueous extract phase is admixed with additional water.
  • the water content of the aqueous extract phase is increased to about 70 to about 85% by weight and preferably about 75% by weight.
  • the second liquid coal naphtha phase is then separated from the second aqueous phase by conventional methods, such as decantation. Once separated, the second naphtha phase can then be subjected to known conventional processing to produce combustible fuels, such as gasoline.
  • the second aqueous extract phase is treated to thereby regenerate the aqueous alkanolamine composition and to obtain a phase containing the separated hydroxy-substituted hydrocarbons and/or mercapto-substituted hydrocarbons and carboxylic acids if present, from the initial liquid coal naphthas.
  • the preferred method for the separation is to contact the second aqueous phase with an acidic gas, such as CO 2 or H 2 S.
  • the amount of acidic gas employed is such as to reduce the pn of the aqueous composition to about 8 or less.
  • the pressure employed is about 5 to about 15 psig.
  • the hydroxy-substituted hydrocarbons and/or mercapto-substituted hydrocarbons if desired, can be separated into individ- . ualized products.
  • the impurities being phenolic material, such as phenol, orthocresol, metacresol, paracresol, and the xylenols
  • the mixture can be distilled into phenol, orthocresol, and a mixture of metal and paracresol.
  • Paracresol at the present is the most important cresol from a commercial standpoint and is useful in disinfectants, dyestuffs, dyes, synthetic polymers, pharmaceuticals, and pic- ments.
  • Metacresol can be used in the preparation of sythetic resins, as developers in photography, for ore flotation, and for various xylenols which, if desired, can be employed as solvents, pharmaceuticals, insecticides, fungicides, lubricants, gasoline, and as peptizing agents for synthetic rubbers.
  • Figure 1 is a flow diagram of a sequence of steps for carrying out the process of the present invention.
  • the alkanolamine/water composition and liquid coal naphthas are introduced into extracter 23 via conduits 21 and 22, respectively.
  • Treated coal naphtha is removed from extracter 23 via conduit 24 and can be conveyed for example to treating processes represented by 25 for conversion to gasoline which is removed via conduit 26.
  • An aqueous portion containing the alkanolamine and hydroxy and/or mercapto hydrocarbons is removed from extratcr 23 via conduit 27. Additional water is added to this aqueous portion via conduit 31.
  • An oil phase is then separated from an aqueous phase via conduit 36.
  • the aqueous alkanolamine composition can then be regenerated and separated from the hydroxy and/or mercapto-substituted hydrocarbons such as by contacting the aqueous composition in vessel 29 with an acidic gas such as CO 2 or H 2 S or S0 2 introduced via conduti 28.
  • an acidic gas such as CO 2 or H 2 S or S0 2 introduced via conduti 28.
  • the impurities from the naphtha e.g., the hydroxy and/or mercapto substituted hydrocarbons
  • conduit 37 e.g., the hydroxy and/or mercapto substituted hydrocarbons
  • the aqueous alkanolamine and acidic gas mixture can be conveyed to a stripper column 32 via conduit 30 wherein the aqueous alkanolamine composition is removed via conduit 33 and the acidic gas is removed via conduit 34.
  • the aqueous alkanolamine 33 can be recycled and conveyed to conduit 21.
  • the acidic gas can be recycled and conveyed to conduit 26.
  • a bottoms is removed from column 32 via conduit 35.
  • liquid coal naphtha About 17,230 ml of liquid coal naphtha are charged to the bottom portion of a York-Scheibel Column of the type illustrated in Figure 2 via conduit 2.
  • the feed rate of the liquid coal naphtha is about 48.9 ml per minute.
  • About 2,770 ml of a 50% by volume aqueous monoethanolamine solution is introduced into the column via conduit 1 at the upper part of the column.
  • the flow rate of the aqueous monoethanolamine composition is about 7.9 ml per minute.
  • the column is operated at a temperature of about 75°F and a stirrer rate of about 275 rpms.
  • the ratio of the liquid coal naphthas to the monoethanclamine is about 12.4:1.
  • the time of operation is about 352.4 minutes.
  • the liquid coal naphthas employed as feed have the following properties:
  • the liquid coal raffinate has the following properties:
  • the aqueous phase is contacted with additional water in order to increase the water concentration to about 75% by volume of the composition. This requires about 2770 ml of water.
  • additional water Upon admixing of the additional water, an oil phase and water phase develop.
  • the oil phase is separated from the water phase and amounts to about 3.5% of the volume of the aqueous composition and consists of additional liquid coal naphthas.
  • aqueous phase is then contacted with carbon dioxide gas until the pH is about 8. This results in a phenolic phase and an aqueous monoethanolamine phase which are readily separated.
  • Coal liquid naphtha containing fractions boiling up to about 380°F is contacted with a 50/50 weight percent monoethanolamine-water composition.
  • the volume ratio of the hydro- bon / monoethanolamine present in the aqueous composition is about 10:1.
  • the extractions are carried out in separatory funnels and in three stages. The three stages are an effort to duplicate a continuous counter current extraction column.
  • Table I summarizes the volume extracted as the phenols mixture. This value is the difference between the weight of raffinate reccvered and the weight of charge to the experiment after the extraction using three stages.
  • Table II summarizes the isomer distribution of the phenols and the grams present and the grams of phenol extracted. The amount. of phenols and isomer distribution are determined by G.C.
  • Example 2A is repeated except that a 30/70 weight percent ratio monoethanolamine-water composition is employed. The results obtained are presented in Tables I - III hereinbelow.
  • Example 2A is repeated except that a 70/30 weight percent ratio monoethanolamine-water composition is employed.
  • the results obtained are presented in Tables I - III hereinbelow.
  • Table III summarizes the results of the extractions or the extraction efficiency of the three different concentrations of the MEA/H 2 O mixtures on the respective isomers present.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Extraction Or Liquid Replacement (AREA)
EP82109463A 1981-10-28 1982-10-13 Verfahren zur Entfernung Hydroxy und/oder Merkapto substituierten Kohlenwasserstoffen aus Kohleflüssigkeiten Withdrawn EP0077977A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US315823 1981-10-28
US06/315,823 US4382855A (en) 1981-10-28 1981-10-28 Process for removal of hydroxy- and/or mercapto-substituted hydrocarbons from coal liquids

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EP0077977A2 true EP0077977A2 (de) 1983-05-04
EP0077977A3 EP0077977A3 (de) 1983-12-07

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EP82109463A Withdrawn EP0077977A3 (de) 1981-10-28 1982-10-13 Verfahren zur Entfernung Hydroxy und/oder Merkapto substituierten Kohlenwasserstoffen aus Kohleflüssigkeiten

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US (1) US4382855A (de)
EP (1) EP0077977A3 (de)
CA (1) CA1166272A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123395A3 (en) * 1983-03-28 1986-05-07 Betz Europe, Inc. Method and composition for neutralizing acidic components in petroleum refining units
EP0227259A1 (de) * 1985-10-28 1987-07-01 The Dow Chemical Company Beseitigung von Schwefel aus Kohlenwasserstoffen
EP0538738A3 (en) * 1991-10-15 1993-05-12 General Sekiyu Kabushiki Kaisha Desulfurization and denitration of light oil by extraction

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4601738A (en) * 1982-05-03 1986-07-22 El Paso Hydrocarbons Company Process for freeze protection and purification of natural gas liquid product streams produced by the Mehra process
JPH0637622B2 (ja) * 1986-07-04 1994-05-18 栗田工業株式会社 石油精製又は石油プロセス用中和剤
US9162952B2 (en) 2013-11-19 2015-10-20 Uop Llc Process for purifying products from coal tar

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126331A (en) * 1964-03-24 Purifying hydrocarbons
US2152720A (en) * 1936-09-28 1939-04-04 Shell Dev Process for removing acid components from hydrocarbon distillates
US2238201A (en) * 1937-09-18 1941-04-15 Carbide & Carbon Chem Corp Purification of hydrocarbon liquids
US2311342A (en) * 1941-03-15 1943-02-16 Standard Oil Dev Co Sulphur removal from hydrocarbons
US2383416A (en) * 1943-03-12 1945-08-21 Girdler Corp Process of removing hydrogen sulphide from hydrocarbon liquids
US2497954A (en) * 1947-10-03 1950-02-21 Standard Oil Dev Co Method for removing emulsifying agents from amine solution
US2797188A (en) * 1953-12-04 1957-06-25 Dow Chemical Co Refining petroleum with an alkanolamine absorbent and reactivation of the spent alkanol amine
US2971906A (en) * 1955-08-25 1961-02-14 Shell Oil Co Process for removing nitrogenous compounds from hydrocarbon oils
US3291728A (en) * 1963-12-27 1966-12-13 Hydrocarbon Research Inc Solvent extraction
CS171199B2 (de) * 1964-09-29 1976-10-29
US3282830A (en) * 1965-06-08 1966-11-01 Hydrocarbon Research Inc Solvent extraction of aromatics with an alkanol amine solvent
US3719587A (en) * 1970-06-30 1973-03-06 Exxon Research Engineering Co Purging and washing coal naphtha to remove dihydrogen sulfide and basic nitrogen
US3847800A (en) * 1973-08-06 1974-11-12 Kvb Eng Inc Method for removing sulfur and nitrogen in petroleum oils
SU757526A1 (ru) * 1978-09-11 1980-08-23 Inst Chimii Bashkirskogo Способ выделения меркаптанов из нефтяных - дистиллятов 1

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0123395A3 (en) * 1983-03-28 1986-05-07 Betz Europe, Inc. Method and composition for neutralizing acidic components in petroleum refining units
EP0227259A1 (de) * 1985-10-28 1987-07-01 The Dow Chemical Company Beseitigung von Schwefel aus Kohlenwasserstoffen
EP0538738A3 (en) * 1991-10-15 1993-05-12 General Sekiyu Kabushiki Kaisha Desulfurization and denitration of light oil by extraction
EP0653477B1 (de) * 1991-10-15 1997-03-12 General Sekiyu Kabushiki Kaisha Verwendung eines organischen Lösungsmittels zur Denitrierung eines leichten Öls durch Extraktion

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US4382855A (en) 1983-05-10
CA1166272A (en) 1984-04-24
EP0077977A3 (de) 1983-12-07

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